research communications

Acta Cryst. (2018). E74, 1467–1470 https://doi.org/10.1107/S2056989018012409 1467

Received 21 August 2018

Accepted 3 September 2018

Edited by A. J. Lough, University of Toronto,

Canada

Keywords: crystal structure; organic light-emit-

ting diode; organometallic light emitter; lumi-

nescent iridium complex; polymorph;

cyclometallated iridium complex.

CCDC references: 1865394; 1865393

Supporting information: this article has

supporting information at journals.iucr.org/e

The crystal structure of bis{3,5-difluoro-2-[4-(2,4,6-trimethylphenyl)pyridin-2-yl]phenyl}(picolinato)-iridium(III) and its 4-tert-butylpyridin-2-yl analogue

Robert D. Sannera and Victor G. Young Jrb*

aLawrence Livermore National Laboratory, Livermore, CA 94550, USA, and bDepartment of Chemistry, University of

Minnesota, Minneapolis, MN 55455, USA. *Correspondence e-mail: vyoung@umn.edu

The crystal structures of bis{3,5-difluoro-2-[4-(2,4,6-trimethylphenyl)pyridin-2-

yl]phenyl-�2N,C 1}(picolinato-�2N,O)iridium(III), [Ir(C20H16F2N)2(C6H4NO2)],

1, and bis[2-(4-tert-butylpyridin-2-yl)-3,5-difluorophenyl-�2N,C 1](picolinato-

�2N,O)iridium(III), [Ir(C15H14F2N)2(C6H4NO2)], 2, are presented herein. These

phosphorescent cyclometallated iridium(III) compounds have been structurally

investigated in order to better understand the nature of their blue-shifted

emssions while maintaining high quantum yields. Compound 1 exhibits

substantial twisting of the mesitylene rings out of the plane of the attached

pyridine ring, with dihedral angles of 67.0 (1) and 78.7 (1)� between the best mean

planes. For both compounds, the contribution of disordered solvent molecule(s)

was removed using the SQUEEZE [Spek (2015). Acta Cryst. C71, 9–18] routine in

PLATON [Spek (2015). Acta Cryst. C71, 9–18]. These solvent molecules are not

considered in the given chemical formula and other crystal data.

1. Chemical context

Phosphorescent cyclometallated iridium(III) compounds have

been investigated for a variety of applications, including solar

cells (Kim et al., 2016), sensors (Marın-Suarez et al., 2012),

bioimaging (Zhang et al., 2015), and scintillators (Bertrand et

al., 2015). However, their most widespread use stems from

their electrophosphorescence and research in this area has

focused on their use in organic light-emitting diodes (OLED)

(Choy et al., 2014; Chi & Chou, 2010; Fu et al., 2011). The most

widely studied blue-emitting iridium complex for this purpose

is bis[2-(4,6-difluorophenyl)pyridinato]iridium(III) picolinate,

or FIrpic (Baranoff & Curchod, 2015). As part of our synthesis

program for plastic scintillators (Rupert et al., 2012; Cherepy

et al., 2015), we have prepared and structurally characterized

several blue-emitting iridium complexes (Sanner et al., 2016).

A recent study by another group has examined the attachment

of alkyl or aryl groups to the pyridine ring of the (difluoro-

phenyl)pyridinate ligand in FIrpic (Kozhevnikov et al., 2013),

resulting in enhanced quantum efficiency, while maintaining

the sky-blue color of the parent complex. We have prepared

and structurally characterized two of those complexes to

examine the structural basis for their superior behavior. We

report herein the crystal structures of bis{3,5-difluoro-2-[4-

(2,4,6-trimethylphenyl)pyridin-2-yl]phenyl-�2N,C1}(picolinato-

�2N,O)iridium(III), 1, and bis[2-(4-tert-butylpyridin-2-yl)-3,5-

difluorophenyl-�2N,C1](picolinato-�2N,O)iridium(III), 2. The

molecular structure of 2 has been reported previously (Laskar

et al., 2006), however, the structure reported below is a new

polymorph.

ISSN 2056-9890

2. Structural commentary

The molecular structure of complexes 1 and 2 have been

confirmed by X-ray crystallography and displacement ellip-

soid diagrams are shown in Figs. 1 and 2. Both complexes

exhibit the same distorted octahedral geometry with two

bidentate phenylpyridine ligands (coordinated through the

pyridine N atom and a phenyl C atom) and one bidentate

pyridine-2-carboxylate ligand, also known as 2-picolinate

(coordinated through the pyridine N atom and a carboxylate

O atom). The iridium-bound N atoms of the phenylpyridine

ligands are trans to each other, while the phenyl C atoms

bound to iridium are cis. The two ligated atoms in the picoli-

nate ligand are then trans to the phenyl C atoms of the

phenylpyridine ligand. The trans effect of the phenyl groups is

most clearly seen when comparing Ir—N bond lengths. Thus,

the Ir—N(picolinate) bond is on average 0.1 A longer than the

Ir—N(phenylpyridine) bond due to its trans disposition to the

phenyl group. Although there is no such intramolecular

comparison available for the picolinate Ir—O bond (which is

also trans to a phenyl group), we note that the Ir—O bond

length in both these molecules is 2.16 A. This compares with

the shorter value of 2.09 A reported in the Cambridge

Structural Database (CSD; Version 5.39, May 2018, with three

updates; Groom et al., 2016) for an Ir—O bond, again illus-

trating the trans effect of the phenyl group in these molecules.

The C—Ir—N ‘bite’ angle for the phenylpyridine ligand

averages 80.8 (4)� for these complexes, while the N—Ir—O

angle for the picolinate ligand is somewhat smaller at 76.7 (2)�.

The phenyl and pyridine rings in each phenylpyridine ligand

are slightly twisted with respect to each other across the C—C

bond linking the two rings. The dihedral angle between the

best planes for the two rings is in the range 6–10� in these

molecules. A feature of special interest in 1 is the dihedral

angle between the plane of the pyridine ring and that of the

attached mesityl group, e.g. between the N1/C7–C11 ring and

the C12–C17 ring. These values are 67.0 (1) and 78.7 (1)� for

the two mesityl–phenylpyridine ligands in 1. The presence of

two ortho-methyl groups on the mesitylene (e.g. C18 and C20)

presumably causes this large twist of the mesityl ring out of the

1468 Sanner and Young Jr � [Ir(C20H16F2N)2(C6H4NO2)] and [Ir(C15H14F2N)2(C6H4NO2)] Acta Cryst. (2018). E74, 1467–1470

research communications

Figure 2The molecular structure of 2, with the atom labeling and displacementellipsoids drawn at the 50% probability level. H atoms have beenremoved for clarity.

Figure 1The molecular structure of 1, with the atom labeling and displacementellipsoids drawn at the 50% probability level. H atoms have beenremoved for clarity.

plane of the attached pyridine ring. This possibility has been

proposed (Kozhevnikov et al., 2013) as an explanation for the

blue emission of 1 since it minimizes the �-conjugation

between the mesityl and pyridine rings which would otherwise

lead to red-shifted emission. Our results confirm the structural

basis for this proposal.

3. Supramolecular features

Neither complex forms any significant supramolecular inter-

actions with neighboring molecules.

4. Database survey

The molecular structure of 2 has been reported previously

(Laskar et al., 2006; CSD refcode CEHGOM); however, the

structure reported below is a new polymorph as a solvate. A

search of the CSD (Groom et al., 2016) provided no additional

crystal structures related to 1 or 2.

5. Synthesis and crystallization

The title compounds were prepared as described previously

(Kozhevnikov et al., 2013). Diffraction-quality crystals of 1

were obtained by slow evaporation using methanol as solvent,

while 2 utilized a 1:2 (v/v) methyl ethyl ketone–hexane

mixture as solvent.

6. Refinement

Crystal data, data collection and structure refinement details

are summarized in Table 1. All H atoms were placed in

calculated positions and refined as riding atoms; for aryl H

atoms, C—H = 0.95 A and Uiso(H) = 1.2Ueq(C), and for methyl

H atoms, C—H = 0.98 A and Uiso(H) = 1.5Ueq(C). Both

specimens used for this study contained badly disordered

solvent of crystallization. Specimens for compound 1 tended

to lose solvent during mounting. The initial structure solution

appeared to be either a methanol trisolvate or a methanol/

water disolvate, where all three molecules were concatenated

through hydrogen bonds to the O2 hydrogen-bond acceptor.

Only one methanol solvent molecule was clearly indicated, but

it had considerable translational displacements toward a

putative compositionally disordered methanol/water site. The

last member of this chain was likely a methanol, but it was

pathologically disordered. The SQUEEZE routine (Spek,

2015) from PLATON (Spek, 2009) was applied to this disor-

dered solvent region since in least-squares no reasonable

disorder model could be achieved. Void spaces centered at (0,

0, 0) and (0, 0.5, 0.5) totaling 727 A3 were found to contain an

electron count of 177. This electron count would correspond

to approximately ten methanol molecules per unit cell. The

specimen for compound 2 did not appear to lose solvent

during mounting. The initial structure solution found the

expected compound and a region near an inversion center

composed of unknown solvent. The peaks in the difference

Fourier map did not provide any reasonable solvent molecule

(or molecules) after numerous attempts. The SQUEEZE

research communications

Acta Cryst. (2018). E74, 1467–1470 Sanner and Young Jr � [Ir(C20H16F2N)2(C6H4NO2)] and [Ir(C15H14F2N)2(C6H4NO2)] 1469

Table 1Experimental details.

1 2

Crystal dataChemical formula [Ir(C20H16F2N)2(C6H4NO2)] [Ir(C15H14F2N)2(C6H4NO2)]Mr 930.98 806.84Crystal system, space group Monoclinic, P21/c Monoclinic, P21/cTemperature (K) 100 100a, b, c (A) 15.1582 (12), 12.3530 (9), 24.2353 (17) 14.7519 (7), 14.4121 (7), 18.5425 (8)� (�) 106.374 (3) 104.7761 (19)V (A3) 4354.0 (6) 3811.9 (3)Z 4 4Radiation type Mo K� Mo K�� (mm�1) 3.12 3.55Crystal size (mm) 0.12 � 0.12 � 0.12 0.15 � 0.13 � 0.04

Data collectionDiffractometer Area Bruker PHOTON-II CPAD Area Bruker PHOTON-II CPADAbsorption correction Multi-scan (SADABS; Bruker, 2014) Multi-scan (SADABS; Bruker, 2014)Tmin, Tmax 0.576, 0.746 0.370, 0.433No. of measured, independent and observed

[I > 2�(I)] reflections74054, 13464, 11535 81284, 11662, 9342

Rint 0.042 0.049(sin �/)max (A�1) 0.718 0.715

RefinementR[F 2 > 2�(F 2)], wR(F 2), S 0.030, 0.063, 1.10 0.025, 0.057, 1.02No. of reflections 13464 11662No. of parameters 512 421H-atom treatment H-atom parameters constrained H-atom parameters constrained�max, �min (e A�3) 2.62, �1.64 0.98, �1.39

Computer programs: APEX3 (Bruker, 2014), SAINT (Bruker, 2014), SHELXT2014 (Sheldrick, 2015a), SHELXL2018 (Sheldrick, 2015b) and SHELXTL (Sheldrick, 2008).

routine from PLATON was applied to this disordered solvent

region. Void spaces centered at (0, 0, 0.5) and (0, 0.5, 0)

totaling 954.7 A3 were found to contain an electron count of

203. This electron count would correspond to approximately

four methyl ethyl ketone or hexane molecules per unit cell.

Acknowledgements

We thank the X-Ray Crystallographic Laboratory, LeClaire-

Dow Instrumentation Facility, Department of Chemistry,

University of Minnesota, for its contribution. The authors

would like to acknowledge Mr James T. Moore and the X-Ray

Crystallography course CHEM5755 for assistance in collecting

single-crystal diffraction data on 1 and 2. The Bruker AXS D8

Venture diffractometer was purchased through a grant from

NSF/MRI and the University of Minnesota.

Funding information

Funding for this research was provided by: US DOE, Lawr-

ence Livermore National Laboratory (contract No. DE-AC52-

07NA27344); US DOE, National Nuclear Security Adminis-

tration, Defense Nuclear Non-proliferation Research and

Development (contract No. DE-AC03-76SF00098); NSF/MRI

(award No. 1229400).

References

Baranoff, E. & Curchod, B. F. E. (2015). Dalton Trans. 44, 8318–8329.Bertrand, G. H. V., Hamel, M., Normand, S. & Sguerra, F. (2015).

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Bruker (2014). APEX3, SAINT and SADABS. Bruker AXS Inc.,Madison, Wisconsin, USA.

Cherepy, N. J., Sanner, R. D., Beck, P. R., Swanberg, E. L., Tillotson,T. M., Payne, S. A. & Hurlbut, C. R. (2015). Nucl. Instrum. MethodsPhys. Res. A, 778, 126–132.

Chi, Y. & Chou, P.-T. (2010). Chem. Soc. Rev. 39, 638–655.Choy, W. C. H., Chan, W. K. & Yuan, Y. (2014). Adv. Mater. 26, 5368–

5399.Fu, H., Cheng, Y.-M., Chou, P.-T. & Chi, Y. (2011). Mater. Today, 14,

472–479.Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta

Cryst. B72, 171–179.Kim, H.-T., Seo, J. H., Ahn, J. H., Baek, M.-J., Um, H.-D., Lee, S., Roh,

D.-H., Yum, J.-H., Shin, T. J., Seo, K. & Kwon, T.-H. (2016). ACSEnergy Lett. 1, 991–999.

Kozhevnikov, V. N., Zheng, Y., Clough, M., Al-Attar, H. A., Griffiths,G. C., Abdullah, K., Raisys, S., Jankus, V., Bryce, M. R. &Monkman, A. P. (2013). Chem. Mater. 25, 2352–2358.

Laskar, I. R., Hsu, S.-F. & Chen, T.-M. (2006). Polyhedron, 25, 1167–1176.

Marın-Suarez, M., Curchod, B. F. E., Tavernelli, I., Rothlisberger, U.,Scopelliti, R., Jung, I., Di Censo, D., Gratzel, M., Fernandez-Sanchez, J. F., Fernandez-Gutierrez, A., Nazeeruddin, M. K. &Baranoff, E. (2012). Chem. Mater. 24, 2330–2338.

Rupert, B. L., Cherepy, N. J., Sturm, B. W., Sanner, R. D. & Payne, S.A. (2012). EPL, 97, article No. 22002.

Sanner, R. D., Cherepy, N. J. & Young, V. G. Jr (2016). Inorg. Chim.Acta, 440, 165–171.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.Spek, A. L. (2009). Acta Cryst. D65, 148–155.Spek, A. L. (2015). Acta Cryst. C71, 9–18.Zhang, K. Y., Liu, H.-W., Tang, M.-C., Choi, A. W.-T., Zhu, N., Wei,

X.-G., Lau, K.-C. & Lo, K. K.-W. (2015). Inorg. Chem. 54, 6582–6593.

1470 Sanner and Young Jr � [Ir(C20H16F2N)2(C6H4NO2)] and [Ir(C15H14F2N)2(C6H4NO2)] Acta Cryst. (2018). E74, 1467–1470

research communications

supporting information

sup-1Acta Cryst. (2018). E74, 1467-1470

supporting information

Acta Cryst. (2018). E74, 1467-1470 [https://doi.org/10.1107/S2056989018012409]

The crystal structure of bis{3,5-difluoro-2-[4-(2,4,6-trimethylphenyl)pyridin-2-

yl]phenyl}(picolinato)iridium(III) and its 4-tert-butylpyridin-2-yl analogue

Robert D. Sanner and Victor G. Young

Computing details

For both structures, data collection: APEX3 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction:

SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine

structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare

material for publication: SHELXTL (Sheldrick, 2008).

Bis{3,5-difluoro-2-[4-(2,4,6-trimethylphenyl)pyridin-2-yl]phenyl-κ2N,C1}(picolinato-κ2N,O)iridium(III) (1)

Crystal data

[Ir(C20H16F2N)2(C6H4NO2)]Mr = 930.98Monoclinic, P21/ca = 15.1582 (12) Åb = 12.3530 (9) Åc = 24.2353 (17) Åβ = 106.374 (3)°V = 4354.0 (6) Å3

Z = 4

F(000) = 1848Dx = 1.420 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 9153 reflectionsθ = 2.5–30.7°µ = 3.12 mm−1

T = 100 KBlock, yellow0.12 × 0.12 × 0.12 mm

Data collection

Area Bruker PHOTON-II CPAD diffractometer

Radiation source: microfocusφ and ω scansAbsorption correction: multi-scan

(SADABS; Bruker, 2014)Tmin = 0.576, Tmax = 0.74674054 measured reflections

13464 independent reflections11535 reflections with I > 2σ(I)Rint = 0.042θmax = 30.7°, θmin = 2.2°h = −21→21k = −17→17l = −30→34

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.030wR(F2) = 0.063S = 1.1013464 reflections512 parameters0 restraints

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrainedw = 1/[σ2(Fo

2) + (0.0107P)2 + 8.8889P] where P = (Fo

2 + 2Fc2)/3

(Δ/σ)max = 0.006Δρmax = 2.62 e Å−3

Δρmin = −1.64 e Å−3

supporting information

sup-2Acta Cryst. (2018). E74, 1467-1470

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

Ir1 0.44048 (2) 0.26980 (2) 0.61437 (2) 0.01790 (3)C1 0.46242 (17) 0.32003 (19) 0.54086 (10) 0.0173 (4)C2 0.39581 (18) 0.3451 (2) 0.48951 (10) 0.0194 (5)H2A 0.332635 0.330991 0.485277 0.023*C3 0.42336 (18) 0.3906 (2) 0.44514 (10) 0.0205 (5)F1 0.35653 (11) 0.42187 (13) 0.39699 (6) 0.0247 (3)C4 0.51336 (19) 0.4086 (2) 0.44628 (10) 0.0204 (5)H4A 0.529744 0.437693 0.414238 0.025*C5 0.57841 (18) 0.3818 (2) 0.49690 (11) 0.0198 (5)F2 0.66758 (11) 0.40260 (14) 0.49956 (7) 0.0273 (3)C6 0.55632 (18) 0.3387 (2) 0.54451 (10) 0.0189 (5)C7 0.62144 (18) 0.3177 (2) 0.60110 (10) 0.0201 (5)C8 0.71651 (19) 0.3190 (2) 0.61409 (11) 0.0236 (5)H8A 0.744865 0.335431 0.584779 0.028*C9 0.77108 (19) 0.2966 (2) 0.66960 (12) 0.0262 (6)C10 0.72713 (19) 0.2742 (3) 0.71159 (11) 0.0279 (6)H10A 0.762028 0.259416 0.750019 0.033*C11 0.63216 (19) 0.2736 (2) 0.69675 (11) 0.0252 (5)H11A 0.602878 0.258211 0.725735 0.030*N1 0.57912 (15) 0.29390 (17) 0.64278 (9) 0.0188 (4)C12 0.8732 (2) 0.2943 (3) 0.68225 (12) 0.0329 (7)C13 0.9183 (3) 0.1955 (3) 0.68471 (16) 0.0467 (9)C14 1.0147 (3) 0.1968 (4) 0.69527 (19) 0.0615 (12)H14A 1.046683 0.129977 0.697781 0.074*C15 1.0634 (3) 0.2912 (5) 0.70197 (17) 0.0625 (13)C16 1.0171 (3) 0.3869 (4) 0.6987 (2) 0.0671 (13)H16A 1.050763 0.452802 0.703217 0.080*C17 0.9212 (2) 0.3909 (4) 0.68900 (18) 0.0521 (10)C18 0.8665 (3) 0.0910 (4) 0.6755 (3) 0.0792 (16)H18A 0.908129 0.031842 0.672623 0.119*H18B 0.816111 0.095033 0.639851 0.119*H18C 0.841417 0.077452 0.707948 0.119*C19 1.1680 (3) 0.2894 (6) 0.7136 (3) 0.099 (2)H19A 1.189898 0.362465 0.708880 0.148*H19B 1.184515 0.240147 0.686417 0.148*H19C 1.196445 0.264378 0.752993 0.148*C20 0.8725 (3) 0.4990 (4) 0.6840 (3) 0.0834 (18)H20A 0.916920 0.555588 0.701383 0.125*H20B 0.824712 0.495448 0.704071 0.125*

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sup-3Acta Cryst. (2018). E74, 1467-1470

H20C 0.844154 0.515872 0.643344 0.125*C21 0.45657 (18) 0.1194 (2) 0.58964 (10) 0.0199 (5)C22 0.53758 (19) 0.0587 (2) 0.60259 (11) 0.0228 (5)H22A 0.592843 0.087662 0.627112 0.027*C23 0.5370 (2) −0.0434 (2) 0.57965 (11) 0.0244 (5)F3 0.61738 (12) −0.09986 (14) 0.59174 (7) 0.0312 (4)C24 0.4596 (2) −0.0919 (2) 0.54407 (12) 0.0265 (6)H24A 0.461298 −0.162441 0.528785 0.032*C25 0.3798 (2) −0.0319 (2) 0.53206 (12) 0.0256 (5)F4 0.30307 (12) −0.07915 (14) 0.49674 (8) 0.0347 (4)C26 0.37433 (19) 0.0718 (2) 0.55362 (11) 0.0214 (5)C27 0.29216 (18) 0.1404 (2) 0.54264 (11) 0.0216 (5)C28 0.20602 (19) 0.1192 (2) 0.50477 (12) 0.0255 (5)H28A 0.196735 0.054324 0.482825 0.031*C29 0.13299 (19) 0.1916 (2) 0.49849 (12) 0.0264 (5)C30 0.14919 (19) 0.2857 (2) 0.53145 (13) 0.0273 (6)H30A 0.100800 0.335859 0.529270 0.033*C31 0.23655 (19) 0.3057 (2) 0.56749 (12) 0.0242 (5)H31A 0.247382 0.371254 0.588827 0.029*N2 0.30662 (15) 0.23538 (18) 0.57334 (9) 0.0207 (4)C32 0.0424 (2) 0.1647 (2) 0.45704 (13) 0.0290 (6)C33 0.0347 (2) 0.1588 (3) 0.39791 (13) 0.0329 (6)C34 −0.0469 (2) 0.1216 (3) 0.36043 (14) 0.0386 (7)H34A −0.051883 0.117025 0.320534 0.046*C35 −0.1215 (2) 0.0909 (3) 0.37967 (14) 0.0364 (7)C36 −0.1140 (2) 0.1033 (2) 0.43762 (14) 0.0333 (7)H36A −0.165574 0.086533 0.451004 0.040*C37 −0.0340 (2) 0.1391 (2) 0.47677 (13) 0.0302 (6)C38 0.1131 (3) 0.1942 (3) 0.37436 (15) 0.0438 (8)H38A 0.089207 0.209260 0.333131 0.066*H38B 0.159140 0.136384 0.380381 0.066*H38C 0.141607 0.259789 0.394411 0.066*C39 −0.2074 (2) 0.0433 (3) 0.33887 (16) 0.0483 (9)H39A −0.193167 0.016486 0.304286 0.072*H39B −0.255023 0.099212 0.328086 0.072*H39C −0.229634 −0.016696 0.357818 0.072*C40 −0.0297 (2) 0.1475 (3) 0.53984 (13) 0.0355 (7)H40A 0.022382 0.105043 0.562743 0.053*H40B −0.086911 0.119468 0.545677 0.053*H40C −0.021905 0.223488 0.551894 0.053*O1 0.41561 (13) 0.43013 (14) 0.64265 (7) 0.0207 (4)O2 0.39443 (15) 0.52154 (16) 0.71775 (8) 0.0289 (4)C41 0.40599 (17) 0.4372 (2) 0.69325 (11) 0.0203 (5)C42 0.40885 (17) 0.3319 (2) 0.72522 (10) 0.0198 (5)C43 0.3988 (2) 0.3291 (2) 0.78032 (11) 0.0271 (6)H43A 0.391480 0.394281 0.799356 0.033*C44 0.3995 (2) 0.2302 (3) 0.80721 (13) 0.0337 (6)H44A 0.392203 0.226377 0.844824 0.040*

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sup-4Acta Cryst. (2018). E74, 1467-1470

C45 0.4111 (2) 0.1365 (2) 0.77822 (12) 0.0305 (6)H45A 0.411129 0.067594 0.795591 0.037*C46 0.42253 (19) 0.1451 (2) 0.72369 (12) 0.0254 (5)H46A 0.431422 0.081050 0.704225 0.031*N3 0.42147 (15) 0.24099 (18) 0.69746 (9) 0.0202 (4)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Ir1 0.02447 (5) 0.01372 (4) 0.01498 (4) −0.00063 (4) 0.00470 (3) 0.00034 (4)C1 0.0281 (12) 0.0089 (10) 0.0156 (10) −0.0001 (9) 0.0073 (9) −0.0003 (8)C2 0.0256 (12) 0.0123 (11) 0.0188 (11) −0.0008 (9) 0.0040 (9) −0.0030 (8)C3 0.0308 (13) 0.0120 (11) 0.0162 (11) 0.0032 (9) 0.0028 (9) −0.0031 (8)F1 0.0314 (8) 0.0233 (8) 0.0167 (7) 0.0049 (6) 0.0024 (6) 0.0025 (6)C4 0.0334 (14) 0.0125 (11) 0.0163 (11) 0.0016 (10) 0.0084 (10) −0.0002 (8)C5 0.0254 (12) 0.0138 (11) 0.0210 (12) 0.0003 (9) 0.0075 (9) −0.0021 (9)F2 0.0279 (8) 0.0294 (9) 0.0253 (8) 0.0004 (7) 0.0088 (6) 0.0032 (6)C6 0.0268 (12) 0.0126 (11) 0.0161 (11) 0.0005 (9) 0.0041 (9) −0.0019 (8)C7 0.0280 (13) 0.0115 (11) 0.0189 (11) 0.0009 (9) 0.0037 (9) −0.0008 (8)C8 0.0281 (13) 0.0198 (13) 0.0221 (12) 0.0026 (10) 0.0060 (10) 0.0015 (10)C9 0.0260 (13) 0.0234 (14) 0.0254 (13) 0.0031 (10) 0.0012 (10) −0.0017 (10)C10 0.0295 (13) 0.0304 (14) 0.0187 (12) 0.0047 (12) −0.0015 (10) 0.0015 (11)C11 0.0311 (13) 0.0252 (13) 0.0177 (11) −0.0015 (11) 0.0044 (10) −0.0005 (10)N1 0.0229 (10) 0.0149 (10) 0.0169 (9) 0.0013 (8) 0.0029 (8) 0.0001 (7)C12 0.0240 (13) 0.048 (2) 0.0226 (13) 0.0070 (12) −0.0004 (10) 0.0045 (12)C13 0.0387 (19) 0.055 (2) 0.049 (2) 0.0164 (17) 0.0151 (16) 0.0065 (17)C14 0.041 (2) 0.084 (3) 0.059 (3) 0.029 (2) 0.0128 (18) 0.013 (2)C15 0.0294 (18) 0.110 (4) 0.043 (2) 0.012 (2) 0.0014 (15) 0.011 (2)C16 0.034 (2) 0.082 (4) 0.073 (3) −0.011 (2) −0.0059 (19) 0.007 (3)C17 0.0271 (17) 0.060 (3) 0.058 (2) −0.0040 (16) −0.0064 (15) 0.0019 (19)C18 0.065 (3) 0.044 (3) 0.134 (5) 0.027 (2) 0.037 (3) 0.003 (3)C19 0.032 (2) 0.171 (7) 0.086 (4) 0.017 (3) 0.006 (2) 0.030 (4)C20 0.047 (3) 0.045 (3) 0.140 (5) −0.017 (2) −0.003 (3) −0.003 (3)C21 0.0295 (13) 0.0172 (12) 0.0141 (11) −0.0012 (10) 0.0080 (9) 0.0037 (8)C22 0.0312 (13) 0.0175 (12) 0.0188 (12) 0.0012 (10) 0.0057 (10) 0.0031 (9)C23 0.0338 (14) 0.0178 (12) 0.0229 (12) 0.0053 (10) 0.0102 (11) 0.0041 (9)F3 0.0392 (10) 0.0225 (9) 0.0320 (9) 0.0117 (7) 0.0100 (7) 0.0033 (7)C24 0.0418 (16) 0.0132 (12) 0.0272 (13) −0.0027 (11) 0.0140 (12) −0.0018 (10)C25 0.0335 (14) 0.0185 (13) 0.0247 (13) −0.0057 (11) 0.0080 (11) −0.0021 (10)F4 0.0357 (10) 0.0211 (9) 0.0444 (10) −0.0075 (7) 0.0065 (8) −0.0116 (7)C26 0.0304 (13) 0.0135 (11) 0.0209 (12) −0.0019 (10) 0.0082 (10) 0.0014 (9)C27 0.0273 (13) 0.0156 (12) 0.0228 (12) −0.0024 (10) 0.0084 (10) 0.0018 (9)C28 0.0316 (14) 0.0185 (13) 0.0246 (13) −0.0053 (11) 0.0051 (10) −0.0012 (10)C29 0.0276 (13) 0.0228 (13) 0.0273 (13) −0.0035 (11) 0.0051 (10) 0.0046 (11)C30 0.0245 (13) 0.0200 (14) 0.0360 (15) 0.0012 (10) 0.0065 (11) 0.0020 (11)C31 0.0290 (13) 0.0180 (12) 0.0271 (13) −0.0012 (10) 0.0104 (10) 0.0004 (10)N2 0.0257 (10) 0.0152 (9) 0.0213 (10) −0.0024 (9) 0.0067 (8) 0.0017 (8)C32 0.0292 (14) 0.0213 (14) 0.0323 (15) −0.0022 (11) 0.0019 (11) 0.0042 (11)

supporting information

sup-5Acta Cryst. (2018). E74, 1467-1470

C33 0.0357 (16) 0.0237 (14) 0.0353 (16) −0.0007 (12) 0.0036 (12) 0.0036 (12)C34 0.0440 (18) 0.0295 (17) 0.0333 (16) 0.0027 (14) −0.0036 (13) 0.0032 (13)C35 0.0317 (16) 0.0266 (16) 0.0410 (17) 0.0003 (12) −0.0061 (13) 0.0037 (13)C36 0.0246 (14) 0.0242 (15) 0.0448 (18) −0.0016 (11) −0.0007 (12) 0.0071 (12)C37 0.0286 (14) 0.0227 (14) 0.0360 (15) −0.0001 (11) 0.0040 (11) 0.0071 (11)C38 0.053 (2) 0.044 (2) 0.0325 (17) −0.0121 (17) 0.0089 (15) 0.0014 (14)C39 0.0387 (19) 0.041 (2) 0.051 (2) −0.0039 (15) −0.0115 (15) −0.0008 (16)C40 0.0303 (15) 0.0360 (18) 0.0374 (17) −0.0040 (13) 0.0052 (12) 0.0049 (13)O1 0.0297 (10) 0.0143 (8) 0.0185 (8) −0.0007 (7) 0.0075 (7) −0.0003 (6)O2 0.0448 (12) 0.0199 (10) 0.0237 (10) 0.0001 (9) 0.0122 (9) −0.0034 (7)C41 0.0211 (12) 0.0188 (12) 0.0203 (12) −0.0038 (9) 0.0048 (9) −0.0008 (9)C42 0.0203 (11) 0.0200 (13) 0.0184 (11) 0.0000 (9) 0.0042 (9) 0.0009 (9)C43 0.0359 (15) 0.0274 (15) 0.0198 (12) 0.0032 (12) 0.0107 (11) 0.0021 (10)C44 0.0468 (17) 0.0340 (16) 0.0241 (13) 0.0067 (14) 0.0163 (12) 0.0077 (12)C45 0.0392 (16) 0.0256 (15) 0.0279 (14) 0.0057 (12) 0.0113 (12) 0.0128 (11)C46 0.0320 (14) 0.0195 (13) 0.0255 (13) 0.0035 (11) 0.0094 (11) 0.0033 (10)N3 0.0243 (10) 0.0178 (11) 0.0179 (9) −0.0002 (8) 0.0049 (8) 0.0029 (8)

Geometric parameters (Å, º)

Ir1—C21 1.988 (3) C23—F3 1.363 (3)Ir1—C1 2.001 (2) C23—C24 1.381 (4)Ir1—N2 2.037 (2) C24—C25 1.378 (4)Ir1—N1 2.040 (2) C24—H24A 0.9500Ir1—N3 2.143 (2) C25—F4 1.365 (3)Ir1—O1 2.1633 (18) C25—C26 1.395 (4)C1—C2 1.398 (3) C26—C27 1.468 (4)C1—C6 1.420 (4) C27—N2 1.373 (3)C2—C3 1.378 (4) C27—C28 1.393 (4)C2—H2A 0.9500 C28—C29 1.398 (4)C3—F1 1.368 (3) C28—H28A 0.9500C3—C4 1.375 (4) C29—C30 1.392 (4)C4—C5 1.380 (3) C29—C32 1.493 (4)C4—H4A 0.9500 C30—C31 1.388 (4)C5—F2 1.359 (3) C30—H30A 0.9500C5—C6 1.394 (3) C31—N2 1.348 (4)C6—C7 1.470 (3) C31—H31A 0.9500C7—N1 1.372 (3) C32—C33 1.407 (4)C7—C8 1.386 (4) C32—C37 1.408 (4)C8—C9 1.394 (4) C33—C34 1.390 (4)C8—H8A 0.9500 C33—C38 1.521 (5)C9—C10 1.392 (4) C34—C35 1.392 (5)C9—C12 1.491 (4) C34—H34A 0.9500C10—C11 1.382 (4) C35—C36 1.385 (5)C10—H10A 0.9500 C35—C39 1.514 (4)C11—N1 1.352 (3) C36—C37 1.385 (4)C11—H11A 0.9500 C36—H36A 0.9500C12—C17 1.383 (5) C37—C40 1.515 (4)

supporting information

sup-6Acta Cryst. (2018). E74, 1467-1470

C12—C13 1.392 (5) C38—H38A 0.9800C13—C14 1.411 (5) C38—H38B 0.9800C13—C18 1.495 (6) C38—H38C 0.9800C14—C15 1.365 (7) C39—H39A 0.9800C14—H14A 0.9500 C39—H39B 0.9800C15—C16 1.366 (7) C39—H39C 0.9800C15—C19 1.529 (6) C40—H40A 0.9800C16—C17 1.406 (5) C40—H40B 0.9800C16—H16A 0.9500 C40—H40C 0.9800C17—C20 1.514 (6) O1—C41 1.278 (3)C18—H18A 0.9800 O2—C41 1.236 (3)C18—H18B 0.9800 C41—C42 1.508 (4)C18—H18C 0.9800 C42—N3 1.350 (3)C19—H19A 0.9800 C42—C43 1.387 (4)C19—H19B 0.9800 C43—C44 1.383 (4)C19—H19C 0.9800 C43—H43A 0.9500C20—H20A 0.9800 C44—C45 1.390 (4)C20—H20B 0.9800 C44—H44A 0.9500C20—H20C 0.9800 C45—C46 1.384 (4)C21—C22 1.397 (4) C45—H45A 0.9500C21—C26 1.431 (4) C46—N3 1.342 (3)C22—C23 1.377 (4) C46—H46A 0.9500C22—H22A 0.9500

C21—Ir1—C1 87.48 (9) C23—C22—H22A 120.2C21—Ir1—N2 81.24 (10) C21—C22—H22A 120.2C1—Ir1—N2 91.30 (9) F3—C23—C22 118.5 (3)C21—Ir1—N1 92.06 (10) F3—C23—C24 117.6 (2)C1—Ir1—N1 80.87 (9) C22—C23—C24 123.9 (3)N2—Ir1—N1 169.95 (8) C25—C24—C23 116.0 (3)C21—Ir1—N3 100.86 (9) C25—C24—H24A 122.0C1—Ir1—N3 171.25 (9) C23—C24—H24A 122.0N2—Ir1—N3 92.56 (8) F4—C25—C24 116.4 (2)N1—Ir1—N3 96.07 (8) F4—C25—C26 119.8 (3)C21—Ir1—O1 176.51 (9) C24—C25—C26 123.8 (3)C1—Ir1—O1 94.92 (8) C25—C26—C21 118.2 (2)N2—Ir1—O1 96.15 (8) C25—C26—C27 126.8 (2)N1—Ir1—O1 90.83 (8) C21—C26—C27 115.0 (2)N3—Ir1—O1 76.87 (7) N2—C27—C28 119.6 (2)C2—C1—C6 118.6 (2) N2—C27—C26 113.4 (2)C2—C1—Ir1 126.97 (19) C28—C27—C26 126.9 (2)C6—C1—Ir1 114.22 (17) C27—C28—C29 121.2 (3)C3—C2—C1 118.9 (2) C27—C28—H28A 119.4C3—C2—H2A 120.6 C29—C28—H28A 119.4C1—C2—H2A 120.6 C30—C29—C28 117.8 (3)F1—C3—C4 117.6 (2) C30—C29—C32 123.5 (3)F1—C3—C2 117.8 (2) C28—C29—C32 118.7 (3)C4—C3—C2 124.6 (2) C31—C30—C29 119.5 (3)

supporting information

sup-7Acta Cryst. (2018). E74, 1467-1470

C3—C4—C5 115.8 (2) C31—C30—H30A 120.3C3—C4—H4A 122.1 C29—C30—H30A 120.3C5—C4—H4A 122.1 N2—C31—C30 122.4 (3)F2—C5—C4 116.6 (2) N2—C31—H31A 118.8F2—C5—C6 120.0 (2) C30—C31—H31A 118.8C4—C5—C6 123.3 (2) C31—N2—C27 119.5 (2)C5—C6—C1 118.7 (2) C31—N2—Ir1 124.31 (19)C5—C6—C7 125.8 (2) C27—N2—Ir1 115.32 (17)C1—C6—C7 115.3 (2) C33—C32—C37 119.7 (3)N1—C7—C8 120.5 (2) C33—C32—C29 119.6 (3)N1—C7—C6 113.2 (2) C37—C32—C29 120.7 (3)C8—C7—C6 126.3 (2) C34—C33—C32 119.1 (3)C7—C8—C9 120.9 (3) C34—C33—C38 119.7 (3)C7—C8—H8A 119.6 C32—C33—C38 121.2 (3)C9—C8—H8A 119.6 C33—C34—C35 121.9 (3)C10—C9—C8 118.0 (3) C33—C34—H34A 119.0C10—C9—C12 121.9 (2) C35—C34—H34A 119.0C8—C9—C12 120.1 (3) C36—C35—C34 117.8 (3)C11—C10—C9 119.3 (2) C36—C35—C39 121.0 (3)C11—C10—H10A 120.4 C34—C35—C39 121.2 (3)C9—C10—H10A 120.4 C37—C36—C35 122.4 (3)N1—C11—C10 122.9 (3) C37—C36—H36A 118.8N1—C11—H11A 118.6 C35—C36—H36A 118.8C10—C11—H11A 118.6 C36—C37—C32 118.9 (3)C11—N1—C7 118.6 (2) C36—C37—C40 119.6 (3)C11—N1—Ir1 125.07 (18) C32—C37—C40 121.5 (3)C7—N1—Ir1 115.69 (16) C33—C38—H38A 109.5C17—C12—C13 121.0 (3) C33—C38—H38B 109.5C17—C12—C9 119.3 (3) H38A—C38—H38B 109.5C13—C12—C9 119.6 (3) C33—C38—H38C 109.5C12—C13—C14 118.0 (4) H38A—C38—H38C 109.5C12—C13—C18 121.4 (3) H38B—C38—H38C 109.5C14—C13—C18 120.6 (4) C35—C39—H39A 109.5C15—C14—C13 121.9 (4) C35—C39—H39B 109.5C15—C14—H14A 119.0 H39A—C39—H39B 109.5C13—C14—H14A 119.0 C35—C39—H39C 109.5C14—C15—C16 118.8 (4) H39A—C39—H39C 109.5C14—C15—C19 120.5 (5) H39B—C39—H39C 109.5C16—C15—C19 120.8 (5) C37—C40—H40A 109.5C15—C16—C17 122.0 (5) C37—C40—H40B 109.5C15—C16—H16A 119.0 H40A—C40—H40B 109.5C17—C16—H16A 119.0 C37—C40—H40C 109.5C12—C17—C16 118.3 (4) H40A—C40—H40C 109.5C12—C17—C20 121.5 (3) H40B—C40—H40C 109.5C16—C17—C20 120.2 (4) C41—O1—Ir1 116.32 (16)C13—C18—H18A 109.5 O2—C41—O1 126.0 (2)C13—C18—H18B 109.5 O2—C41—C42 117.9 (2)H18A—C18—H18B 109.5 O1—C41—C42 116.1 (2)

supporting information

sup-8Acta Cryst. (2018). E74, 1467-1470

C13—C18—H18C 109.5 N3—C42—C43 121.9 (2)H18A—C18—H18C 109.5 N3—C42—C41 116.7 (2)H18B—C18—H18C 109.5 C43—C42—C41 121.4 (2)C15—C19—H19A 109.5 C44—C43—C42 119.2 (3)C15—C19—H19B 109.5 C44—C43—H43A 120.4H19A—C19—H19B 109.5 C42—C43—H43A 120.4C15—C19—H19C 109.5 C43—C44—C45 118.8 (3)H19A—C19—H19C 109.5 C43—C44—H44A 120.6H19B—C19—H19C 109.5 C45—C44—H44A 120.6C17—C20—H20A 109.5 C46—C45—C44 119.1 (3)C17—C20—H20B 109.5 C46—C45—H45A 120.4H20A—C20—H20B 109.5 C44—C45—H45A 120.4C17—C20—H20C 109.5 N3—C46—C45 122.1 (3)H20A—C20—H20C 109.5 N3—C46—H46A 118.9H20B—C20—H20C 109.5 C45—C46—H46A 118.9C22—C21—C26 118.4 (2) C46—N3—C42 118.8 (2)C22—C21—Ir1 127.5 (2) C46—N3—Ir1 127.22 (18)C26—C21—Ir1 114.08 (19) C42—N3—Ir1 113.94 (16)C23—C22—C21 119.7 (3)

C6—C1—C2—C3 −2.3 (3) C24—C25—C26—C21 0.9 (4)Ir1—C1—C2—C3 172.49 (18) F4—C25—C26—C27 0.1 (4)C1—C2—C3—F1 −175.2 (2) C24—C25—C26—C27 179.8 (3)C1—C2—C3—C4 3.6 (4) C22—C21—C26—C25 −1.6 (4)F1—C3—C4—C5 176.3 (2) Ir1—C21—C26—C25 177.24 (19)C2—C3—C4—C5 −2.4 (4) C22—C21—C26—C27 179.3 (2)C3—C4—C5—F2 −177.7 (2) Ir1—C21—C26—C27 −1.8 (3)C3—C4—C5—C6 0.2 (4) C25—C26—C27—N2 175.4 (2)F2—C5—C6—C1 178.7 (2) C21—C26—C27—N2 −5.7 (3)C4—C5—C6—C1 0.8 (4) C25—C26—C27—C28 −6.0 (4)F2—C5—C6—C7 3.7 (4) C21—C26—C27—C28 172.9 (2)C4—C5—C6—C7 −174.2 (2) N2—C27—C28—C29 −1.7 (4)C2—C1—C6—C5 0.3 (3) C26—C27—C28—C29 179.8 (3)Ir1—C1—C6—C5 −175.16 (18) C27—C28—C29—C30 −0.1 (4)C2—C1—C6—C7 175.8 (2) C27—C28—C29—C32 179.7 (3)Ir1—C1—C6—C7 0.3 (3) C28—C29—C30—C31 2.0 (4)C5—C6—C7—N1 168.8 (2) C32—C29—C30—C31 −177.9 (3)C1—C6—C7—N1 −6.3 (3) C29—C30—C31—N2 −2.1 (4)C5—C6—C7—C8 −12.0 (4) C30—C31—N2—C27 0.2 (4)C1—C6—C7—C8 172.9 (2) C30—C31—N2—Ir1 169.2 (2)N1—C7—C8—C9 −0.2 (4) C28—C27—N2—C31 1.6 (4)C6—C7—C8—C9 −179.3 (2) C26—C27—N2—C31 −179.6 (2)C7—C8—C9—C10 −0.7 (4) C28—C27—N2—Ir1 −168.25 (19)C7—C8—C9—C12 177.7 (3) C26—C27—N2—Ir1 10.5 (3)C8—C9—C10—C11 0.8 (4) C30—C29—C32—C33 115.0 (3)C12—C9—C10—C11 −177.6 (3) C28—C29—C32—C33 −64.9 (4)C9—C10—C11—N1 0.0 (5) C30—C29—C32—C37 −68.7 (4)C10—C11—N1—C7 −1.0 (4) C28—C29—C32—C37 111.5 (3)

supporting information

sup-9Acta Cryst. (2018). E74, 1467-1470

C10—C11—N1—Ir1 169.1 (2) C37—C32—C33—C34 −3.7 (5)C8—C7—N1—C11 1.1 (4) C29—C32—C33—C34 172.6 (3)C6—C7—N1—C11 −179.7 (2) C37—C32—C33—C38 175.1 (3)C8—C7—N1—Ir1 −169.93 (19) C29—C32—C33—C38 −8.5 (5)C6—C7—N1—Ir1 9.3 (3) C32—C33—C34—C35 0.5 (5)C10—C9—C12—C17 −103.3 (4) C38—C33—C34—C35 −178.3 (3)C8—C9—C12—C17 78.3 (4) C33—C34—C35—C36 3.0 (5)C10—C9—C12—C13 79.3 (4) C33—C34—C35—C39 −175.7 (3)C8—C9—C12—C13 −99.1 (4) C34—C35—C36—C37 −3.5 (5)C17—C12—C13—C14 1.1 (5) C39—C35—C36—C37 175.2 (3)C9—C12—C13—C14 178.3 (3) C35—C36—C37—C32 0.4 (5)C17—C12—C13—C18 −177.9 (4) C35—C36—C37—C40 −178.1 (3)C9—C12—C13—C18 −0.6 (5) C33—C32—C37—C36 3.3 (4)C12—C13—C14—C15 −1.1 (6) C29—C32—C37—C36 −173.1 (3)C18—C13—C14—C15 177.8 (4) C33—C32—C37—C40 −178.2 (3)C13—C14—C15—C16 0.5 (7) C29—C32—C37—C40 5.5 (4)C13—C14—C15—C19 179.7 (4) Ir1—O1—C41—O2 177.5 (2)C14—C15—C16—C17 0.3 (7) Ir1—O1—C41—C42 −2.8 (3)C19—C15—C16—C17 −179.0 (4) O2—C41—C42—N3 179.9 (2)C13—C12—C17—C16 −0.3 (6) O1—C41—C42—N3 0.2 (3)C9—C12—C17—C16 −177.6 (3) O2—C41—C42—C43 0.1 (4)C13—C12—C17—C20 177.5 (4) O1—C41—C42—C43 −179.7 (2)C9—C12—C17—C20 0.2 (6) N3—C42—C43—C44 −1.5 (4)C15—C16—C17—C12 −0.4 (7) C41—C42—C43—C44 178.3 (3)C15—C16—C17—C20 −178.2 (5) C42—C43—C44—C45 0.5 (5)C26—C21—C22—C23 1.4 (4) C43—C44—C45—C46 0.7 (5)Ir1—C21—C22—C23 −177.24 (19) C44—C45—C46—N3 −1.0 (5)C21—C22—C23—F3 178.3 (2) C45—C46—N3—C42 0.0 (4)C21—C22—C23—C24 −0.5 (4) C45—C46—N3—Ir1 178.7 (2)F3—C23—C24—C25 −179.1 (2) C43—C42—N3—C46 1.3 (4)C22—C23—C24—C25 −0.2 (4) C41—C42—N3—C46 −178.6 (2)C23—C24—C25—F4 179.8 (2) C43—C42—N3—Ir1 −177.6 (2)C23—C24—C25—C26 0.0 (4) C41—C42—N3—Ir1 2.5 (3)F4—C25—C26—C21 −178.9 (2)

Bis[2-(4-tert-butylpyridin-2-yl)-3,5-difluorophenyl-κ2N,C1](picolinato-κ2N,O)iridium(III) (2)

Crystal data

[Ir(C15H14F2N)2(C6H4NO2)]Mr = 806.84Monoclinic, P21/ca = 14.7519 (7) Åb = 14.4121 (7) Åc = 18.5425 (8) Åβ = 104.7761 (19)°V = 3811.9 (3) Å3

Z = 4

F(000) = 1592Dx = 1.406 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 2779 reflectionsθ = 2.8–30.1°µ = 3.55 mm−1

T = 100 KPlate, yellow0.15 × 0.13 × 0.04 mm

supporting information

sup-10Acta Cryst. (2018). E74, 1467-1470

Data collection

Area Bruker PHOTON-II CPAD diffractometer

Radiation source: microfocusφ and ω scansAbsorption correction: multi-scan

(SADABS; Bruker, 2014)Tmin = 0.370, Tmax = 0.43381284 measured reflections

11662 independent reflections9342 reflections with I > 2σ(I)Rint = 0.049θmax = 30.6°, θmin = 2.4°h = −21→21k = −20→20l = −26→19

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.025wR(F2) = 0.057S = 1.0211662 reflections421 parameters0 restraints

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrainedw = 1/[σ2(Fo

2) + (0.0242P)2 + 2.756P] where P = (Fo

2 + 2Fc2)/3

(Δ/σ)max = 0.002Δρmax = 0.98 e Å−3

Δρmin = −1.39 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

Ir1 0.30539 (2) 0.53433 (2) 0.67510 (2) 0.01538 (3)C1 0.23415 (16) 0.65492 (15) 0.65931 (13) 0.0171 (4)C2 0.17630 (18) 0.68813 (17) 0.59293 (14) 0.0231 (5)H2 0.167851 0.653112 0.548305 0.028*C3 0.13158 (19) 0.77159 (18) 0.59224 (16) 0.0280 (6)F1 0.07501 (14) 0.80352 (12) 0.52723 (10) 0.0479 (5)C4 0.13985 (18) 0.82624 (17) 0.65481 (16) 0.0275 (6)H4 0.108614 0.884197 0.652714 0.033*C5 0.19550 (18) 0.79214 (16) 0.71984 (15) 0.0239 (5)F2 0.20190 (12) 0.84419 (11) 0.78251 (9) 0.0348 (4)C6 0.24427 (16) 0.70822 (16) 0.72467 (13) 0.0179 (5)C7 0.30904 (17) 0.67197 (16) 0.79204 (13) 0.0192 (5)C8 0.34074 (18) 0.71680 (17) 0.86029 (14) 0.0227 (5)H8 0.314210 0.775053 0.867499 0.027*C9 0.41011 (19) 0.67912 (18) 0.91841 (14) 0.0249 (5)C10 0.4435 (2) 0.5920 (2) 0.90580 (14) 0.0297 (6)H10 0.489611 0.562161 0.943949 0.036*C11 0.4095 (2) 0.54871 (18) 0.83770 (14) 0.0266 (6)H11 0.432831 0.488843 0.830709 0.032*N1 0.34539 (14) 0.58692 (13) 0.78110 (11) 0.0190 (4)C12 0.4463 (2) 0.7337 (2) 0.99013 (15) 0.0312 (6)C13 0.4881 (2) 0.8263 (2) 0.97229 (17) 0.0392 (7)

supporting information

sup-11Acta Cryst. (2018). E74, 1467-1470

H13A 0.512994 0.860843 1.018614 0.059*H13B 0.439081 0.862971 0.938708 0.059*H13C 0.538732 0.813863 0.948183 0.059*C14 0.5224 (2) 0.6809 (2) 1.04678 (16) 0.0456 (8)H14A 0.544789 0.718886 1.091608 0.068*H14B 0.574806 0.667242 1.024868 0.068*H14C 0.496480 0.622629 1.060121 0.068*C15 0.3636 (2) 0.7541 (2) 1.02501 (16) 0.0355 (7)H15A 0.385539 0.792902 1.069460 0.053*H15B 0.338844 0.695600 1.039034 0.053*H15C 0.313999 0.786809 0.988629 0.053*C16 0.18532 (17) 0.47689 (15) 0.68282 (14) 0.0198 (5)C17 0.15357 (19) 0.46982 (19) 0.74756 (16) 0.0279 (6)H17 0.189174 0.494662 0.793538 0.034*C18 0.0694 (2) 0.4259 (2) 0.74288 (17) 0.0325 (6)F3 0.03862 (13) 0.41878 (15) 0.80583 (10) 0.0486 (5)C19 0.0135 (2) 0.3893 (2) 0.67848 (19) 0.0396 (7)H19 −0.044204 0.359379 0.677508 0.048*C20 0.0456 (2) 0.3983 (2) 0.61536 (18) 0.0351 (7)F4 −0.01075 (13) 0.36506 (15) 0.55072 (11) 0.0529 (6)C21 0.13079 (19) 0.43920 (17) 0.61503 (15) 0.0242 (5)C22 0.17271 (18) 0.44401 (17) 0.55140 (15) 0.0219 (5)C23 0.13701 (18) 0.40646 (18) 0.48020 (15) 0.0267 (6)H23 0.077070 0.377730 0.468464 0.032*C24 0.18727 (17) 0.41028 (17) 0.42637 (14) 0.0224 (5)C25 0.27440 (17) 0.45626 (17) 0.44603 (14) 0.0218 (5)H25 0.311171 0.461624 0.410983 0.026*C26 0.30581 (17) 0.49330 (16) 0.51629 (14) 0.0196 (5)H26 0.364411 0.524625 0.528415 0.023*N2 0.25766 (14) 0.48739 (13) 0.56872 (11) 0.0177 (4)C27 0.15441 (19) 0.36300 (19) 0.35017 (15) 0.0272 (6)C28 0.0537 (2) 0.3279 (2) 0.33600 (17) 0.0367 (7)H28A 0.034009 0.301118 0.285838 0.055*H28B 0.012219 0.379662 0.340076 0.055*H28C 0.050216 0.280341 0.372987 0.055*C29 0.1604 (2) 0.4314 (2) 0.28779 (16) 0.0347 (7)H29A 0.140783 0.400165 0.239377 0.052*H29B 0.225128 0.453235 0.295702 0.052*H29C 0.119114 0.484491 0.288601 0.052*C30 0.2200 (2) 0.2813 (2) 0.34824 (18) 0.0399 (7)H30A 0.199692 0.249467 0.300129 0.060*H30B 0.218259 0.237926 0.388538 0.060*H30C 0.284138 0.304327 0.354822 0.060*O1 0.43862 (11) 0.58218 (10) 0.66085 (9) 0.0163 (3)O2 0.58841 (12) 0.54150 (12) 0.67624 (11) 0.0254 (4)C31 0.50763 (17) 0.52575 (15) 0.67930 (12) 0.0169 (4)C32 0.48442 (17) 0.43140 (16) 0.70654 (12) 0.0170 (4)C33 0.55271 (19) 0.36654 (17) 0.73644 (14) 0.0227 (5)

supporting information

sup-12Acta Cryst. (2018). E74, 1467-1470

H33 0.616864 0.379203 0.739843 0.027*C34 0.5259 (2) 0.28231 (17) 0.76150 (15) 0.0262 (6)H34 0.571751 0.237641 0.783980 0.031*C35 0.4321 (2) 0.26449 (17) 0.75335 (14) 0.0255 (6)H35 0.412206 0.206312 0.767920 0.031*C36 0.36739 (19) 0.33247 (16) 0.72366 (13) 0.0224 (5)H36 0.302752 0.320269 0.718450 0.027*N3 0.39283 (14) 0.41561 (12) 0.70182 (10) 0.0167 (4)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Ir1 0.01640 (5) 0.01245 (4) 0.01887 (4) 0.00043 (4) 0.00740 (3) −0.00049 (4)C1 0.0156 (11) 0.0118 (9) 0.0256 (11) 0.0016 (8) 0.0083 (10) 0.0007 (9)C2 0.0211 (13) 0.0208 (11) 0.0271 (12) −0.0005 (10) 0.0056 (11) −0.0017 (10)C3 0.0196 (13) 0.0263 (13) 0.0346 (15) 0.0043 (10) 0.0003 (11) 0.0020 (11)F1 0.0514 (12) 0.0343 (9) 0.0438 (11) 0.0202 (9) −0.0142 (9) 0.0006 (8)C4 0.0202 (13) 0.0170 (11) 0.0457 (16) 0.0063 (10) 0.0089 (12) 0.0002 (11)C5 0.0221 (13) 0.0162 (11) 0.0357 (14) 0.0003 (9) 0.0115 (11) −0.0066 (10)F2 0.0370 (10) 0.0268 (8) 0.0407 (9) 0.0108 (7) 0.0101 (8) −0.0110 (7)C6 0.0137 (11) 0.0167 (10) 0.0251 (12) 0.0005 (8) 0.0081 (10) −0.0010 (9)C7 0.0181 (12) 0.0165 (10) 0.0257 (12) −0.0008 (9) 0.0109 (10) −0.0012 (9)C8 0.0278 (14) 0.0192 (11) 0.0244 (12) −0.0002 (10) 0.0127 (11) −0.0029 (9)C9 0.0304 (14) 0.0263 (12) 0.0201 (11) 0.0002 (11) 0.0103 (11) −0.0033 (10)C10 0.0365 (16) 0.0336 (14) 0.0179 (11) 0.0100 (12) 0.0049 (11) 0.0000 (11)C11 0.0354 (15) 0.0236 (13) 0.0230 (12) 0.0100 (11) 0.0113 (11) −0.0006 (10)N1 0.0228 (11) 0.0158 (9) 0.0200 (9) 0.0023 (8) 0.0082 (8) 0.0009 (8)C12 0.0409 (17) 0.0305 (14) 0.0227 (13) −0.0001 (12) 0.0093 (12) −0.0070 (11)C13 0.0423 (19) 0.0450 (17) 0.0319 (15) −0.0131 (15) 0.0126 (14) −0.0134 (13)C14 0.054 (2) 0.052 (2) 0.0246 (14) 0.0127 (17) −0.0003 (15) −0.0107 (14)C15 0.051 (2) 0.0314 (14) 0.0283 (14) −0.0032 (13) 0.0169 (14) −0.0121 (12)C16 0.0175 (11) 0.0149 (10) 0.0297 (12) −0.0007 (9) 0.0112 (10) 0.0020 (9)C17 0.0257 (13) 0.0296 (13) 0.0329 (14) 0.0022 (11) 0.0157 (12) 0.0055 (12)C18 0.0320 (16) 0.0340 (14) 0.0414 (16) 0.0015 (12) 0.0272 (14) 0.0069 (13)F3 0.0412 (11) 0.0680 (13) 0.0474 (11) −0.0049 (10) 0.0309 (9) 0.0113 (10)C19 0.0321 (16) 0.0363 (16) 0.061 (2) −0.0101 (13) 0.0318 (16) −0.0054 (15)C20 0.0263 (15) 0.0348 (15) 0.0487 (17) −0.0131 (12) 0.0181 (13) −0.0139 (14)F4 0.0334 (10) 0.0725 (14) 0.0595 (12) −0.0292 (10) 0.0243 (9) −0.0327 (11)C21 0.0210 (13) 0.0217 (11) 0.0337 (14) −0.0035 (10) 0.0137 (11) −0.0054 (10)C22 0.0177 (12) 0.0202 (11) 0.0292 (13) −0.0023 (9) 0.0087 (10) −0.0058 (10)C23 0.0191 (12) 0.0275 (13) 0.0356 (14) −0.0090 (10) 0.0105 (11) −0.0119 (11)C24 0.0178 (12) 0.0226 (12) 0.0267 (12) −0.0013 (9) 0.0055 (10) −0.0086 (10)C25 0.0189 (12) 0.0236 (12) 0.0251 (12) −0.0026 (10) 0.0097 (10) −0.0054 (10)C26 0.0181 (12) 0.0176 (10) 0.0242 (12) −0.0021 (9) 0.0075 (10) −0.0008 (9)N2 0.0171 (10) 0.0145 (9) 0.0215 (10) 0.0001 (7) 0.0048 (8) −0.0026 (7)C27 0.0217 (13) 0.0320 (13) 0.0278 (13) −0.0047 (11) 0.0059 (11) −0.0113 (11)C28 0.0270 (15) 0.0447 (17) 0.0386 (16) −0.0140 (13) 0.0090 (13) −0.0186 (14)C29 0.0302 (16) 0.0440 (16) 0.0288 (14) −0.0086 (13) 0.0053 (13) −0.0063 (13)

supporting information

sup-13Acta Cryst. (2018). E74, 1467-1470

C30 0.0388 (18) 0.0368 (16) 0.0437 (17) 0.0009 (14) 0.0099 (14) −0.0194 (14)O1 0.0149 (8) 0.0132 (7) 0.0213 (8) −0.0007 (6) 0.0054 (7) 0.0005 (6)O2 0.0187 (9) 0.0244 (9) 0.0351 (10) −0.0003 (7) 0.0108 (8) 0.0033 (8)C31 0.0198 (11) 0.0154 (10) 0.0165 (10) −0.0001 (9) 0.0062 (9) −0.0015 (8)C32 0.0225 (12) 0.0150 (9) 0.0158 (10) 0.0004 (9) 0.0093 (10) −0.0010 (8)C33 0.0241 (13) 0.0218 (11) 0.0243 (12) 0.0069 (10) 0.0102 (11) 0.0036 (10)C34 0.0322 (15) 0.0211 (12) 0.0289 (13) 0.0112 (11) 0.0141 (12) 0.0052 (10)C35 0.0381 (16) 0.0157 (11) 0.0276 (13) 0.0016 (10) 0.0170 (12) 0.0029 (10)C36 0.0299 (14) 0.0171 (11) 0.0240 (12) −0.0028 (10) 0.0137 (11) −0.0017 (9)N3 0.0223 (10) 0.0119 (8) 0.0185 (9) 0.0023 (7) 0.0098 (8) −0.0010 (7)

Geometric parameters (Å, º)

Ir1—C16 1.993 (2) C18—F3 1.360 (3)Ir1—C1 2.013 (2) C18—C19 1.372 (4)Ir1—N2 2.034 (2) C19—C20 1.376 (4)Ir1—N1 2.048 (2) C19—H19 0.9500Ir1—N3 2.1238 (19) C20—F4 1.360 (3)Ir1—O1 2.1617 (16) C20—C21 1.389 (4)C1—C2 1.392 (3) C21—C22 1.467 (4)C1—C6 1.410 (3) C22—N2 1.363 (3)C2—C3 1.370 (3) C22—C23 1.399 (4)C2—H2 0.9500 C23—C24 1.388 (3)C3—F1 1.360 (3) C23—H23 0.9500C3—C4 1.382 (4) C24—C25 1.409 (3)C4—C5 1.365 (4) C24—C27 1.532 (3)C4—H4 0.9500 C25—C26 1.374 (3)C5—F2 1.366 (3) C25—H25 0.9500C5—C6 1.398 (3) C26—N2 1.345 (3)C6—C7 1.462 (3) C26—H26 0.9500C7—N1 1.374 (3) C27—C28 1.528 (4)C7—C8 1.391 (3) C27—C30 1.530 (4)C8—C9 1.393 (4) C27—C29 1.540 (4)C8—H8 0.9500 C28—H28A 0.9800C9—C10 1.391 (4) C28—H28B 0.9800C9—C12 1.520 (4) C28—H28C 0.9800C10—C11 1.382 (4) C29—H29A 0.9800C10—H10 0.9500 C29—H29B 0.9800C11—N1 1.339 (3) C29—H29C 0.9800C11—H11 0.9500 C30—H30A 0.9800C12—C14 1.530 (4) C30—H30B 0.9800C12—C13 1.541 (4) C30—H30C 0.9800C12—C15 1.548 (4) O1—C31 1.280 (3)C13—H13A 0.9800 O2—C31 1.229 (3)C13—H13B 0.9800 C31—C32 1.520 (3)C13—H13C 0.9800 C32—N3 1.351 (3)C14—H14A 0.9800 C32—C33 1.382 (3)C14—H14B 0.9800 C33—C34 1.393 (3)

supporting information

sup-14Acta Cryst. (2018). E74, 1467-1470

C14—H14C 0.9800 C33—H33 0.9500C15—H15A 0.9800 C34—C35 1.377 (4)C15—H15B 0.9800 C34—H34 0.9500C15—H15C 0.9800 C35—C36 1.380 (4)C16—C17 1.399 (3) C35—H35 0.9500C16—C21 1.416 (4) C36—N3 1.348 (3)C17—C18 1.376 (4) C36—H36 0.9500C17—H17 0.9500

C16—Ir1—C1 85.90 (9) C18—C17—H17 120.9C16—Ir1—N2 80.63 (9) C16—C17—H17 120.9C1—Ir1—N2 96.16 (9) F3—C18—C19 117.4 (3)C16—Ir1—N1 97.39 (9) F3—C18—C17 118.3 (3)C1—Ir1—N1 80.33 (9) C19—C18—C17 124.3 (3)N2—Ir1—N1 176.12 (8) C18—C19—C20 116.3 (3)C16—Ir1—N3 98.43 (8) C18—C19—H19 121.9C1—Ir1—N3 173.10 (9) C20—C19—H19 121.9N2—Ir1—N3 89.87 (7) F4—C20—C19 116.8 (3)N1—Ir1—N3 93.73 (7) F4—C20—C21 119.7 (3)C16—Ir1—O1 173.52 (8) C19—C20—C21 123.5 (3)C1—Ir1—O1 99.44 (8) C20—C21—C16 117.9 (2)N2—Ir1—O1 95.06 (7) C20—C21—C22 126.2 (3)N1—Ir1—O1 87.18 (7) C16—C21—C22 115.8 (2)N3—Ir1—O1 76.61 (7) N2—C22—C23 120.1 (2)C2—C1—C6 118.6 (2) N2—C22—C21 112.5 (2)C2—C1—Ir1 127.24 (18) C23—C22—C21 127.3 (2)C6—C1—Ir1 114.10 (17) C24—C23—C22 121.4 (2)C3—C2—C1 119.7 (2) C24—C23—H23 119.3C3—C2—H2 120.2 C22—C23—H23 119.3C1—C2—H2 120.2 C23—C24—C25 116.9 (2)F1—C3—C2 119.4 (2) C23—C24—C27 123.0 (2)F1—C3—C4 117.0 (2) C25—C24—C27 120.1 (2)C2—C3—C4 123.6 (3) C26—C25—C24 119.5 (2)C5—C4—C3 116.2 (2) C26—C25—H25 120.2C5—C4—H4 121.9 C24—C25—H25 120.2C3—C4—H4 121.9 N2—C26—C25 123.2 (2)C4—C5—F2 116.7 (2) N2—C26—H26 118.4C4—C5—C6 123.5 (2) C25—C26—H26 118.4F2—C5—C6 119.8 (2) C26—N2—C22 118.8 (2)C5—C6—C1 118.4 (2) C26—N2—Ir1 124.33 (17)C5—C6—C7 125.3 (2) C22—N2—Ir1 116.81 (16)C1—C6—C7 116.3 (2) C28—C27—C30 109.5 (2)N1—C7—C8 119.7 (2) C28—C27—C24 111.8 (2)N1—C7—C6 112.8 (2) C30—C27—C24 108.1 (2)C8—C7—C6 127.3 (2) C28—C27—C29 108.8 (2)C7—C8—C9 122.2 (2) C30—C27—C29 108.5 (2)C7—C8—H8 118.9 C24—C27—C29 110.0 (2)C9—C8—H8 118.9 C27—C28—H28A 109.5

supporting information

sup-15Acta Cryst. (2018). E74, 1467-1470

C10—C9—C8 116.3 (2) C27—C28—H28B 109.5C10—C9—C12 123.6 (2) H28A—C28—H28B 109.5C8—C9—C12 120.0 (2) C27—C28—H28C 109.5C11—C10—C9 120.0 (2) H28A—C28—H28C 109.5C11—C10—H10 120.0 H28B—C28—H28C 109.5C9—C10—H10 120.0 C27—C29—H29A 109.5N1—C11—C10 123.3 (2) C27—C29—H29B 109.5N1—C11—H11 118.3 H29A—C29—H29B 109.5C10—C11—H11 118.3 C27—C29—H29C 109.5C11—N1—C7 118.4 (2) H29A—C29—H29C 109.5C11—N1—Ir1 124.96 (16) H29B—C29—H29C 109.5C7—N1—Ir1 116.37 (16) C27—C30—H30A 109.5C9—C12—C14 112.1 (2) C27—C30—H30B 109.5C9—C12—C13 109.3 (2) H30A—C30—H30B 109.5C14—C12—C13 108.3 (3) C27—C30—H30C 109.5C9—C12—C15 109.0 (2) H30A—C30—H30C 109.5C14—C12—C15 109.1 (2) H30B—C30—H30C 109.5C13—C12—C15 109.0 (2) C31—O1—Ir1 116.79 (14)C12—C13—H13A 109.5 O2—C31—O1 125.8 (2)C12—C13—H13B 109.5 O2—C31—C32 119.0 (2)H13A—C13—H13B 109.5 O1—C31—C32 115.2 (2)C12—C13—H13C 109.5 N3—C32—C33 121.8 (2)H13A—C13—H13C 109.5 N3—C32—C31 115.8 (2)H13B—C13—H13C 109.5 C33—C32—C31 122.4 (2)C12—C14—H14A 109.5 C32—C33—C34 118.9 (2)C12—C14—H14B 109.5 C32—C33—H33 120.6H14A—C14—H14B 109.5 C34—C33—H33 120.6C12—C14—H14C 109.5 C35—C34—C33 119.3 (2)H14A—C14—H14C 109.5 C35—C34—H34 120.4H14B—C14—H14C 109.5 C33—C34—H34 120.4C12—C15—H15A 109.5 C34—C35—C36 119.0 (2)C12—C15—H15B 109.5 C34—C35—H35 120.5H15A—C15—H15B 109.5 C36—C35—H35 120.5C12—C15—H15C 109.5 N3—C36—C35 122.2 (2)H15A—C15—H15C 109.5 N3—C36—H36 118.9H15B—C15—H15C 109.5 C35—C36—H36 118.9C17—C16—C21 119.7 (2) C36—N3—C32 118.7 (2)C17—C16—Ir1 126.2 (2) C36—N3—Ir1 125.94 (17)C21—C16—Ir1 114.18 (17) C32—N3—Ir1 114.67 (14)C18—C17—C16 118.3 (3)

C6—C1—C2—C3 0.7 (4) C19—C20—C21—C16 −2.7 (5)Ir1—C1—C2—C3 178.94 (19) F4—C20—C21—C22 −5.8 (5)C1—C2—C3—F1 −179.9 (2) C19—C20—C21—C22 174.5 (3)C1—C2—C3—C4 −0.4 (4) C17—C16—C21—C20 1.6 (4)F1—C3—C4—C5 178.8 (2) Ir1—C16—C21—C20 −179.6 (2)C2—C3—C4—C5 −0.7 (4) C17—C16—C21—C22 −175.8 (2)C3—C4—C5—F2 −178.0 (2) Ir1—C16—C21—C22 2.9 (3)

supporting information

sup-16Acta Cryst. (2018). E74, 1467-1470

C3—C4—C5—C6 1.6 (4) C20—C21—C22—N2 −179.0 (3)C4—C5—C6—C1 −1.3 (4) C16—C21—C22—N2 −1.8 (3)F2—C5—C6—C1 178.3 (2) C20—C21—C22—C23 −2.1 (5)C4—C5—C6—C7 176.0 (2) C16—C21—C22—C23 175.2 (3)F2—C5—C6—C7 −4.4 (4) N2—C22—C23—C24 1.5 (4)C2—C1—C6—C5 0.1 (3) C21—C22—C23—C24 −175.3 (3)Ir1—C1—C6—C5 −178.36 (18) C22—C23—C24—C25 −2.0 (4)C2—C1—C6—C7 −177.4 (2) C22—C23—C24—C27 174.7 (2)Ir1—C1—C6—C7 4.1 (3) C23—C24—C25—C26 0.9 (4)C5—C6—C7—N1 178.6 (2) C27—C24—C25—C26 −175.9 (2)C1—C6—C7—N1 −4.1 (3) C24—C25—C26—N2 0.6 (4)C5—C6—C7—C8 −6.7 (4) C25—C26—N2—C22 −1.2 (4)C1—C6—C7—C8 170.6 (2) C25—C26—N2—Ir1 176.09 (18)N1—C7—C8—C9 1.2 (4) C23—C22—N2—C26 0.1 (4)C6—C7—C8—C9 −173.2 (2) C21—C22—N2—C26 177.3 (2)C7—C8—C9—C10 −2.7 (4) C23—C22—N2—Ir1 −177.36 (19)C7—C8—C9—C12 176.3 (2) C21—C22—N2—Ir1 −0.1 (3)C8—C9—C10—C11 1.7 (4) C23—C24—C27—C28 10.5 (4)C12—C9—C10—C11 −177.3 (3) C25—C24—C27—C28 −172.9 (3)C9—C10—C11—N1 0.8 (4) C23—C24—C27—C30 −110.1 (3)C10—C11—N1—C7 −2.4 (4) C25—C24—C27—C30 66.5 (3)C10—C11—N1—Ir1 171.5 (2) C23—C24—C27—C29 131.5 (3)C8—C7—N1—C11 1.4 (3) C25—C24—C27—C29 −51.9 (3)C6—C7—N1—C11 176.5 (2) Ir1—O1—C31—O2 −178.69 (19)C8—C7—N1—Ir1 −173.01 (18) Ir1—O1—C31—C32 1.8 (2)C6—C7—N1—Ir1 2.1 (3) O2—C31—C32—N3 −173.9 (2)C10—C9—C12—C14 −0.8 (4) O1—C31—C32—N3 5.6 (3)C8—C9—C12—C14 −179.7 (3) O2—C31—C32—C33 7.9 (3)C10—C9—C12—C13 119.3 (3) O1—C31—C32—C33 −172.5 (2)C8—C9—C12—C13 −59.6 (3) N3—C32—C33—C34 0.8 (4)C10—C9—C12—C15 −121.6 (3) C31—C32—C33—C34 178.8 (2)C8—C9—C12—C15 59.5 (3) C32—C33—C34—C35 2.4 (4)C21—C16—C17—C18 0.0 (4) C33—C34—C35—C36 −3.0 (4)Ir1—C16—C17—C18 −178.6 (2) C34—C35—C36—N3 0.5 (4)C16—C17—C18—F3 179.8 (2) C35—C36—N3—C32 2.6 (3)C16—C17—C18—C19 −0.8 (4) C35—C36—N3—Ir1 −167.53 (18)F3—C18—C19—C20 179.3 (3) C33—C32—N3—C36 −3.2 (3)C17—C18—C19—C20 −0.1 (5) C31—C32—N3—C36 178.6 (2)C18—C19—C20—F4 −177.8 (3) C33—C32—N3—Ir1 167.98 (18)C18—C19—C20—C21 1.9 (5) C31—C32—N3—Ir1 −10.1 (2)F4—C20—C21—C16 177.0 (3)